JP6629221B2 - Epoxy composition - Google Patents

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit of US Provisional Patent Application No. 61 / 947,900, titled "Epoxy Compositions," filed March 4, 2014, which is hereby incorporated by reference in its entirety. I do.

  Epoxy resins are one of the most important industrial polymers in the world and are used extensively in the manufacture of adhesives, paints and coatings, and matrix resins. The core substrate that is central to the production of epoxy resins is typically 2,2-bis (4-hydroxyphenyl) isopropylidene (bisphenol A). The main monomer used in the epoxy resin industry is the diglycidyl ether of bisphenol A, (2,2-bis (4-glycidyloxyphenyl) propane), which accounts for over 75% of the resins used in industrial applications. Equivalent to. This monomer is usually prepared from 2,2-bis (4-hydroxyphenyl) isopropylidene (bisphenol A) and epichlorohydrin using a strong base such as sodium hydroxide. As an alternative synthetic method, for example, a method of allylating bisphenol A followed by epoxidation has been developed.

  One significant use of epoxy resins derived from the diglycidyl ether of bisphenol A is in glass fiber reinforced as rigid or flexible circuit board substrates used in various industrial and consumer electronic products and components. In the laminate. These materials must be refractory to meet safety requirements. The approach to making these materials refractory has been to use various additives, such as brominated compounds, phosphorus-containing compounds, aluminum derivatives, melamine cyanurate, metal phosphinates, and combinations thereof. . Due to environmental considerations, some of the more commonly used halogenated flame retardants have been banned because they can leach into the environment and are toxic . As with most polymeric additives, other flame retardants suffer from the same problem, many of which are toxic, and have all been host Easy to leach from. Therefore, there is a need to make epoxy-based resins fire resistant in a practical, cost effective and environmentally friendly manner.

Previously disclosed processes for preparing flame retardant epoxy resins have focused on the reaction of the epoxy resin with a flame retardant additive or curing agent or chain extender. An approach that produces an epoxy-based monomer, oligomer, polymer, or copolymer that is inherently flame retardant is ideal. Phosphonate polymers, copolymers, oligomers and cooligomers having a wide range of chemical structures which may contain reactive end groups, such as hydroxyl groups, are known. However, the prior art disclosing the reaction of bisphenol A and epichlorohydrin with sodium hydroxide base is not applicable to phosphonate monomers or polymers, copolymers, oligomers or cooligomers. Because the use of strong bases to carry out the synthesis causes hydrolysis of the phosphonate groups, resulting in chain cleavage (and thereby a reduction in molecular weight) as well as phosphonic acid groups, and also causes other undesirable reactions. This results in a complex mixture of products.
Prior art document information related to the invention of this application includes the following (including documents cited at the international stage after the international filing date and documents cited when transiting to another country).
(Prior art documents)
(Patent document)
(Patent Document 1) US Patent Application Publication No. 2005/0020800
(Patent Document 2) US Patent Application Publication No. 2005/0101708
(Patent Document 3) US Patent Application Publication No. 2009/0032770
(Patent Document 4) US Patent Application Publication No. 2009/0192257
(Patent Document 5) US Patent Application Publication No. 2011/0275743
(Patent Document 6) US Patent Application Publication No. 2012/0172500
(Patent Document 7) US Patent Application Publication No. 2012/0238676
(Patent Document 8) US Patent Application Publication No. 2013/0109792
(Patent Document 9) US Patent Application Publication No. 2015/0183992
(Patent Document 10) US Patent Application Publication No. 2015/0240080
(Patent Document 11) US Pat. No. 6,861,499
(Patent Document 12) US Patent No. 7,645,850
(Patent Document 13) US Pat. No. 7,816,486
(Patent Document 14) US Pat. No. 7,838,604
(Patent Document 15) European Patent Application Publication No. 0989788
(Patent Document 16) JP-A-2004-008542
(Patent Document 17) International Publication No. 2009/145224
(Non-patent literature)
(Non-Patent Document 1) Abstract of JP 04008542 A
(Non-Patent Document 2) Database WPI, Week 200982, Thomas Scientific, London, GB; AN 2009-R89803 XP00277399
(Non-Patent Document 3) Extended European Search Report for EP 15757713 dated Sepmber 21, 2017.
(Non-Patent Document 4) International Search Report and Written Opinion for PCT / US2015 / 018721 dated May 19, 2015.

  Various embodiments of the present invention are directed to compositions comprising an epoxy resin, one or more oligomeric phosphonates, and one or more carbodiimides. In some embodiments, the epoxy resin is a novolak type epoxy resin, a cresol-novolak epoxy resin, a triphenol alkane type epoxy resin, an aralkyl type epoxy resin, an aralkyl type epoxy resin having a biphenyl skeleton, a biphenyl type epoxy resin, a dicyclo epoxy resin. Pentadiene type epoxy resin, heterocyclic type epoxy resin, epoxy resin containing naphthalene ring, bisphenol A type epoxy compound, bisphenol F type epoxy compound, stilbene type epoxy resin, trimethylol-propane type epoxy resin, terpene modified epoxy resin, olefin Linear aliphatic epoxy resin, alicyclic epoxy resin, sulfur-containing epoxy resin, phenol novolak epoxy resin obtained by oxidizing the bond with peracetic acid or similar peracid. Containing benzoxazine, for example, bisphenol A type benzoxazine, bisphenol F type benzoxazine, dicyclopentadiene-based benzoxazine, phenolphthalein-based benzoxazine, polyphenol type A benzoxazine, and may be selected from the group consisting of.

  In some embodiments, one or more oligomeric phosphonates may be selected from the group consisting of linear oligomeric phosphonates, branched oligomeric phosphonates, and hyperbranched oligomeric phosphonates. In certain embodiments, one or more oligomeric phosphonates can have from about 60% to about 100% reactive end groups, based on total terminal numbers, and in some embodiments, reactive end groups. The group may be selected from the group consisting of hydroxyl, carboxylic acid, epoxy, glycidyl ether, vinyl, vinyl ester, isopropenyl, isocyanate, and combinations thereof. In certain embodiments, the reactive end group can be hydroxyl.

式中、Ｒは、Ｃ_１〜Ｃ_２０アルキルまたは場合により置換されているアリール基であり、Ｘは、芳香族、シクロアルキル、または脂肪族基であり、ｎは、１〜約１０の整数である；を含む。いくつかの実施形態において、１種以上のオリゴマーホスホネートは、ポリスチレン標準換算でゲル浸透クロマトグラフィによって求められる重量平均分子量が約５００ｇ／モル〜約１８，０００ｇ／モルであってよい。ある特定の実施形態において、１種以上のオリゴマーホスホネートは、約２％〜約１２重量％のリン含有量を有する。特定の実施形態において、組成物は、約５重量％〜約６０重量％の１種以上のオリゴマーホスホネートを含んでいてよい。 In various embodiments, the one or more oligomeric phosphonates can be random or block colooligo (phosphonate ester) or random or block colooligo (phosphonate carbonate). In certain embodiments, one or more oligomeric phosphonate is a compound of formula (I):

Wherein R is C ₁ -C ₂₀ alkyl or an optionally substituted aryl group, X is an aromatic, cycloalkyl, or aliphatic group, and n is an integer from 1 to about 10 Is included. In some embodiments, the one or more oligomeric phosphonates can have a weight average molecular weight as determined by gel permeation chromatography in terms of polystyrene standards of from about 500 g / mol to about 18,000 g / mol. In certain embodiments, one or more oligomeric phosphonates have a phosphorus content of about 2% to about 12% by weight. In certain embodiments, the composition may include from about 5% to about 60% by weight of one or more oligomeric phosphonates.

  In certain embodiments, the one or more carbodiimides are N, N′-dicyclohexylcarbodiimide, N-cyclohexyl-N ′-(2-morpholinoethyl) carbodiimide meth-p-toluenesulfonate, bis (trimethylsilyl) carbodiimide, N -(3-dimethylaminopropyl) -N'-ethylcarbodiimide, N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide hydrochloride, 1,3-di-p-tolylcarbodiimide, N, N'-bis (2-methylphenyl) carbodiimide, N- (tert-butyl) -N ′-[1- (2-chlorophenyl) -1-methylethyl] carbodiimide, N- (tert-butyl) -N ′-(2,6 -Dichlorophenyl) carbodiimide, N-butyl-N '-[1- (2-chloro Eniru) -1-methylethyl] carbodiimide, N, N'-diisopropylcarbodiimide, dicyclohexylcarbodiimide, N- benzyl -N'- cyclohexyl carbodiimide, and may be selected from the group consisting of. In certain embodiments, the composition may include from about 0.01% to about 4.0% by weight of one or more carbodiimides.

  In certain embodiments, the composition may further include one or more antioxidants, and in some embodiments, the antioxidant is a hindered phenolic antioxidant or a phosphite antioxidant, And combinations thereof.

  In some embodiments, the composition comprises chopped or continuous glass fibers, metal fibers, aramid fibers, carbon fibers, or ceramic fibers, surfactants, organic binders, polymer binders, crosslinkers, diluents, Coupling agent, flame retardant, anti-drip agent, fluorinated polyolefin, silicone, lubricant, release agent, pentaerythritol tetrastearate, nucleating agent, antistatic agent, conductive black, carbon nanotube, graphite, graphene, oxidation Graphene, organic antistatic agent, polyalkylene ether, alkyl sulfonate, perfluorosulfonic acid, perfluorobutane, potassium sulfonate, polyamide-containing polymer, catalyst, colorant, ink, dye, antioxidant, stabilizer, and these At least one selected from the group consisting of It may further comprise additional components. In such embodiments, the composition may comprise from about 0.001% to about 1% by weight of each individual additional component.

  Some embodiments are methods for making an epoxy formulation, comprising combining an epoxy resin, a reactive phosphonate oligomer, a carbodiimide, and a catalyst in a solvent to form a mixture; heating the mixture; The method includes: In certain embodiments, the heating may be performed at a temperature from about 20 ° C. to about 250 ° C., and in certain embodiments, the heating may be performed for 60 minutes to 300 minutes. In some embodiments, the heating may be performed at a pressure from about 3 x 103 Pa to about 1 x 10-1 Pa. In various embodiments, the catalyst may be selected from the group consisting of transition metal catalysts, tertiary amines, imidazole containing compounds, and combinations thereof. In some embodiments, the solvent is perfluorohexane, a, a, a-trifluorotoluene, pentane, hexane, cyclohexane, methylcyclohexane, decalin [c + t], dioxane, carbon tetrachloride, Freon-11, benzene, Toluene, triethylamine, carbon disulfide, diisopropyl ether, diethyl ether (ether), t-butyl methyl ether (MTBE), chloroform, ethyl acetate, 1,2-dimethoxyethane (glyme), 2-methoxyethyl ether (diglyme), Tetrahydrofuran (THF), methylene chloride, pyridine (Py), methyl ethyl ketone (MEK), acetone, hexamethylphosphoramide, N-methylpyrrolidinone, nitromethane, dimethylformamide, acetonitrile, Horan, dimethyl sulfoxide, and may be selected from the group consisting of propylene carbonate.

  Further embodiments are directed to articles of manufacture comprising an epoxy resin, one or more reactive oligomeric phosphonates, and one or more carbodiimides. In various embodiments, the article can be a prepreg or laminate; in other embodiments, the article can be a television, computer, laptop computer, tablet computer, printer, mobile phone, video game, DVD, etc. It may be selected from the group consisting of players, stereos, big data servers, and consumer electronics.

式中、Ｒは、Ｃ_１〜Ｃ_２０アルキルまたは場合により置換されているアリール基であり、Ｘは、芳香族、シクロアルキル、または脂肪族基であり、ｎは、１〜約１０の整数である；を含む。ある特定の実施形態において、１種以上のオリゴマーホスホネートは、約２％〜約１２重量％のリン含有量を有する。特定の実施形態において、組成物は、約５重量％〜約６０重量％の１種以上のオリゴマーホスホネートを含んでいてよい。 Other embodiments are directed to compositions containing an epoxy resin, one or more oligomeric phosphonates, and one or more hindered phenolic antioxidants, phosphite antioxidants, or combinations thereof. . In some embodiments, the one or more oligomeric phosphonates have a relative viscosity (η rel) determined by dissolving the sample in dichloromethane at a concentration of 0.5 g polymer / L at 25 ° C. and measuring the solution with a viscometer. Is about 1.01 to about 1.10. In various embodiments, the one or more oligomeric phosphonates have a reactive end group selected from the group consisting of hydroxyl, carboxylic acid, epoxy, glycidyl ether, vinyl, vinyl ester, isopropenyl, isocyanate, and combinations thereof. May have. In certain embodiments, one or more oligomeric phosphonate is a compound of formula (I):

Wherein R is C ₁ -C ₂₀ alkyl or an optionally substituted aryl group, X is an aromatic, cycloalkyl, or aliphatic group, and n is an integer from 1 to about 10 Is included. In certain embodiments, one or more oligomeric phosphonates have a phosphorus content of about 2% to about 12% by weight. In certain embodiments, the composition may include from about 5% to about 60% by weight of one or more oligomeric phosphonates.

  In certain embodiments, the one or more hindered phenolic antioxidants, phosphite antioxidants, or a combination thereof, comprises a sterically hindered phenolic antioxidant, a hydrolytically stable organic phosphite, an organic phosphite. Antioxidants, sterically hindered lactone antioxidants, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis (3- ( 3,5-di-tert-butyl-4-hydroxyphenylpropionamide)), 3,3 ′, 3 ′, 5,5 ′, 5′-hexa-tert-butyl-a, a ′, a ′-( Mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, bis (2,4-ditert-butyl) Butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert- butylphenyl) phosphite, and it may be selected from the group consisting of. In some embodiments, one or more hindered phenolic antioxidants, phosphite antioxidants, or combinations thereof, comprise from about 0.01% to about 1.0% by weight of the composition. Good.

  Before the present compositions and methods are described, it is to be understood that they are not limited to the particular compositions, methodology, or protocols described, as these may vary. It is. Also, the terminology used in the description is for the purpose of describing particular versions or embodiments only, and is not intended to limit the scope limited only by the appended claims. It should also be understood.

  Also, as used herein, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. Note also that it includes references. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosed embodiments, the preferred methods, devices and materials are now described.

  "Optional" or "optional" means that the subsequently described event or condition may or may not occur, and that the statement includes instances where the event occurs and instances where it does not. means.

  "Substantially absent" means that the subsequently described event may occur in less than about 10% of the time, or that the subsequently described component is present in up to about 10% of the total composition. %, Which in some embodiments means up to about 5% in other cases and even up to about 1% in other cases.

  The term "carbonate" as used herein has its conventional meaning, e.g., as a salt of a carboxylic acid, containing the divalent negative radical CO or uncharged ester of the acid. Give things. “Diaryl carbonate” is a carbonate having at least two aryl groups associated with a CO radical, the most principal example of a diaryl carbonate being diphenyl carbonate; however, the definition of diaryl carbonate is not limited to this specific example.

  The term "aromatic dihydroxide" is intended to include any aromatic compound having at least two related hydroxyl substitutions. Examples of "aromatic hydroxides" include, but are not limited to, benzenediol, such as hydroquinone and any bisphenol or bisphenol containing compound.

  The term "alkyl" or "alkyl group" refers to a branched or unbranched hydrocarbon or group of 1 to 20 carbon atoms, such as, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, -Butyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. "Cycloalkyl" or "cycloalkyl group" is a branched or unbranched hydrocarbon in which all or some of the carbons are arranged in a ring, such as, but not limited to, cyclopentyl, cyclohexyl, methylcyclohexyl, and the like. The term "lower alkyl" includes alkyl groups of one to ten carbon atoms.

  The terms "aryl" or "aryl group" refer to a monovalent aromatic hydrocarbon radical or group consisting of one or more fused rings in which at least one ring is essentially aromatic. Aryl may include, but is not limited to, phenyl, naphthyl, biphenyl ring systems, and the like. An aryl group can be unsubstituted or substituted with various substituents including, but not limited to, alkyl, alkenyl, halide, benzyl, alkyl or aromatic ethers, nitro, cyano, and the like, and combinations thereof. Good.

“Substituent” refers to a molecular group that replaces hydrogen in a compound and is not limited to trifluoromethyl, nitro, cyano, C ₁ -C ₂₀ alkyl, aromatic or aryl, halide (F, Cl, Br, _{I), C} 1 ~C ₂₀ alkyl _ether, C 1 _{-C 20} alkyl esters, benzyl halide, benzyl ether, aromatic or aryl ether, hydroxy, alkoxy, amino, alkylamino (-NHR '), dialkylamino (- NR'R "), or other groups that do not interfere with the formation of the diarylalkylphosphonate.

  “Arylol” or “arylol group”, as defined herein, is an aryl group having a hydroxyl (OH) group substituent on the aryl ring. Non-limiting examples of arylols are phenol, naphthol and the like. A wide variety of arylols may be used in embodiments of the present invention, which are commercially available.

  The term "alkanol" or "alkanol group" refers to a compound containing an alkyl of 1 to 20 carbon atoms or further having at least one hydroxyl group substituent. Examples of alkanols include, but are not limited to, methanol, ethanol, 1- and 2-propanol, 1,1-dimethylethanol, hexanol, octanol, and the like. An alkanol group may be optionally substituted by a substituent as described above.

  The term "alkenol" or "alkenol group" refers to a compound containing an alkene of 2 to 20 carbon atoms or further having at least one hydroxyl group substituent. The hydroxyls may be arranged in any isomeric structure (cis or trans). Alkenols may be further substituted by one or more substituents described above and may be used in place of alkanols in some embodiments of the present invention. Alkenols are known to those skilled in the art and many are readily available commercially.

  The terms "flame retardant," "flame resistant," "fire resistant," or "fire resistant," as used herein, means that the composition exhibits a limiting oxygen index (LOI) of at least 27. Means "Flame retardancy", "flame resistance", "fire resistance", or "fire resistance" may also be tested by measuring afterburning time according to the UL test (Subject 94). In this test, the tested materials are given a UL-94V-0, UL-94V-1 and UL-94V-2 classification based on the results obtained with 10 test samples. Briefly, the criteria for each of these UL-94-V-classifications are as follows:

  UL-94V-0: The total flaming combustion for each sample after removal of the ignition flame must not exceed 10 seconds, and the total flaming combustion for 5 samples must not exceed 50 seconds. None of the test samples shall emit any drip that ignites the absorbent cotton.

  UL-94V-1: The total flaming combustion for each sample after removal of the ignition flame must not exceed 30 seconds and the total flaming combustion for 5 samples must not exceed 250 seconds. None of the test samples shall emit any drip that ignites the absorbent cotton.

  UL-94V-2: The total flaming combustion for each sample after removal of the ignition flame must not exceed 30 seconds and the total flaming combustion for 5 samples must not exceed 250 seconds. The test sample may emit flaming particles that ignite the absorbent cotton.

  Fire resistance may be tested by measuring afterburning time. These test methods measure and compare the surface flammability of a material when exposed to a given level of radiant heat energy, and are laboratory test procedures for determining the surface flammability of a material when exposed to a flame. Is given. The test is performed with a small sample, representing the material or assembly to be evaluated as much as possible. The speed at which the flame travels along the surface depends on the physical and thermal properties of the material under test, the product or assembly, the method and orientation of sample attachment, the type and level of flame or heat exposure, the availability of air, and the ambient Depends on the characteristics of the housing. When replaced by different test conditions or end-use conditions are changed, it may not always be possible to predict a change in the measured combustion test response characteristics by or from this test . Therefore, the results are valid only for the burn test exposure conditions described in this procedure.

  The current approach to making polymers flame retardant is to use additives, such as brominated compounds or compounds containing aluminum and / or phosphorus. The use of additives with polymers can adversely affect the processing characteristics and / or mechanical performance of articles made therefrom. Also, some of these compounds are toxic and can leach into the environment over time, making their use less desirable. In some countries, certain brominated additives have been phased out due to environmental concerns.

"Molecular weight" as used herein can be determined by relative viscosity (η _rel ) and / or gel permeation chromatography (GPC). "Relative viscosity" of a polymer is to dissolve a known amount of polymer in a solvent and compare the time it takes for this solution and the pure solvent to travel through a specially designed capillary at a constant temperature. Is measured by Relative viscosity is a measurement that indicates the molecular weight of a polymer. It is also well known that a decrease in relative viscosity indicates a decrease in molecular weight, and that a decrease in molecular weight causes a loss of mechanical properties, such as strength and toughness. GPC gives information about the molecular weight and molecular weight distribution of a polymer. That the molecular weight distribution of the polymer is important for properties such as thermo-oxidative stability (due to different end group amounts), toughness, melt flow, and fire resistance; , Is known to drip more.

  The term "toughness," as used herein, is meant to indicate that a material is resistant to breaking or breaking when subjected to stress or impact. There are various standardized tests available to determine the toughness of a material. Generally, toughness is determined quantitatively using a film or molded sample.

  The phrase "low viscosity at shear", "shear thinning", or similar phrases, as used herein, refer to when a material is melted and subjected to shear, e.g. , Or when the melt is forced by pressure through an object having a die or similar orifice, indicates that the viscosity is reduced. Shear thinning behavior may be left to the blend of materials. Thus, for example, a blend of a hyperbranched oligophosphonate or colooligo (phosphonate carbonate) and a thermoplastic may exhibit shear thinning, but may be linear or lightly branched with the thermoplastic alone or with the thermoplastic. Blends with oligophosphonates or cooligos (phosphonate carbonates) do not show this. Shear thinning can be measured using a standardized method, for example, the Shear Thinning Index (STI). STI refers to the ratio of viscosity at low rpm shear to viscosity at high rpm, which is generally about 10 times lower rotation speed. For example, low shear may be 1 rpm and high shear may be 10 rpm. The higher the STI value, the more shear thinning the material exhibits.

  Some embodiments of the present invention include an epoxy resin; an oligomeric phosphonate, such as a reactive oligophosphonate, a random or block colooligo (phosphonate ester), and a random or block colooligo (phosphonate carbonate); And carbodiimides. In some embodiments, such compositions comprise additional stabilizers, for example, one or more phenolic antioxidants, one or more phosphite antioxidants, or a phenolic antioxidant and one or more phosphites. It may further comprise a combination of phytooxidants. The composition of such embodiments may further comprise, for example, a catalyst and a solvent or other components known in the art. The composition of such embodiments comprises an oligomeric phosphonate, carbodiimide, carbodiimide and phenolic antioxidant or phosphite antioxidant, an oligomeric phosphonate and carbodiimide, or an oligomeric phosphonate, carbodiimide, and a phenolic or phosphite antioxidant. Exhibit improved glass transition temperature, improved heat resistance, and improved flame retardancy over similar compositions lacking. Other embodiments are directed to such compositions and methods for making articles of manufacture composed of or incorporating such compositions.

  Other embodiments of the present invention include: an epoxy resin; an oligomeric phosphonate, such as a reactive oligophosphonate, random or block colooligo (phosphonate ester), and a random or block colooligo (phosphonate carbonate); and one or more phenols. Compositions comprising a neutral antioxidant, one or more phosphite antioxidants, or a combination of a phenolic antioxidant and one or more phosphite antioxidants. In some embodiments, such compositions may further include one or more carbodiimides. The composition of such embodiments may further comprise, for example, a catalyst and a solvent or other components known in the art. The composition of such embodiments comprises an oligomeric phosphonate, carbodiimide, carbodiimide and phenolic antioxidant or phosphite antioxidant, an oligomeric phosphonate and carbodiimide, or an oligomeric phosphonate, carbodiimide, and a phenolic or phosphite antioxidant. Exhibit improved glass transition temperature, improved heat resistance, and improved flame retardancy over similar compositions lacking. Other embodiments are directed to such compositions and methods for making articles of manufacture composed of or incorporating such compositions.

  Antioxidants, such as those described above, are typically incorporated into the polymer system to alter the thermal stability and / or thermal stability of the final compound without altering the base polymer's, for example, mechanical properties or glass transition temperature. Or improve the hydrolytic stability. Surprisingly, it has been found that adding an antioxidant in the presence of a reactive phosphonate oligomer in a thermosetting system such as an epoxy significantly improves the glass transition temperature of the resulting cured formulation. . Thus, compositions comprising an epoxy resin, an oligomeric phosphonate, and one or more phenolic antioxidants, one or more phosphite antioxidants, or combinations thereof, have improved glass transition temperatures, That is, the Tg may be higher than that of the epoxy resin composition containing the oligomer phosphonate alone. For example, in some embodiments, an epoxy composition containing an oligomeric phosphonate and one or more antioxidants has a Tg, as determined by DSC, of greater than 130 ° C, 135 ° C, or 140 ° C, or about 130 ° C. To about 180 <0> C, about 135 <0> C to about 170 <0> C, or any range or individual value encompassed by these exemplary ranges.

  The oligomeric phosphonate of such an embodiment may be linear, branched, or hyperbranched. Generally, the concentration of reactive end groups based on the total number of terminals of the oligomer phosphonate can be high. For example, the oligomeric phosphonate may have a percentage of the total number of termini having reactive end groups of about 80% to 100%, about 85% to about 99%, or about 90% to about 98%. In other embodiments, greater than 90% of all ends of the oligomeric phosphonate may have reactive end groups. In other embodiments, the branched or hyperbranched oligomeric phosphonate has a percentage of the total number of termini having reactive end groups of about 50% to 100%, about 75% to about 95%, or about 80% to about 90%. In certain embodiments, more than 80% of all termini for branched or hyperbranched oligomeric phosphonates may have reactive end groups. The term "reactive end group" is used to describe any chemical site at a branch end that can react with another chemical site. Numerous reactive functional groups are known in the art and are included in the present invention. In certain embodiments, a reactive end group can be a hydroxyl, epoxy, vinyl, or isocyanate group.

  For simplicity, throughout this disclosure, the terms "oligomer phosphonate," "phosphonate oligomer," "oligophosphonate," and the like refer to oligophosphonates, random or block colooligos (phosphonate esters), and random or block colooligos (phosphonate carbonates) Should be construed as referring to any type of oligomer having a phosphonate containing a repeating unit containing Such oligomers encompassed by these terms may be linear, have a relatively small number of branches per oligomer, for example, mildly branched, exhibiting from 1 to about 5 branches, or have a relatively large number of branches, for example, greater than 5 It may be hyperbranched as shown. Although individual types of oligomers may be recruited in certain exemplary embodiments, any of the oligomeric phosphonates described herein can be used in such exemplary embodiments. For example, exemplary descriptions that oligomeric phosphonates are used are linear, mild, which can be oligophosphonates, random or block colooligo (phosphonate esters), and random or block colooligo (phosphonate carbonate) type oligomeric phosphonates. Or hyperbranched oligomeric phosphonates.

  The oligomeric phosphonates of various embodiments may have a low molecular weight. For example, in some embodiments, the molecular weight of the oligophosphonate (weight average molecular weight determined by gel permeation chromatography based on polystyrene calibration) ranges from about 500 g / mol to about 18,000 g / mol, or any within that range. May be used. In other embodiments, the molecular weight range can be from about 1500 g / mol to about 15,000 g / mol, from about 3000 g / mol to about 10,000 g / mol, or any value within the range. In still other embodiments, the molecular weight range is from about 700 g / mol to about 9000 g / mol, from about 1000 g / mol to about 8000 g / mol, from about 3000 g / mol to about 4000 g / mol, or any value within the range. There may be. The lower molecular weight is determined by dissolving the sample in dichloromethane at a concentration of 0.5 g polymer / L at 25 ° C. and measuring the solution with an Ubbelohde viscometer, a relative viscosity (ηrel) of about 1.01 to about 1.20. Or in some embodiments, η rel is about 1.01 to about 1.14, about 1.01 to about 1.10, about 1.02 to about 1.08. Or any value or range encompassed by these exemplary ranges. In certain embodiments, the oligomeric phosphonate included in the compositions of the present invention comprises from about 1.03 to about 1.05 or about 1.04 to about 1.07, or about 1.07 to about 1.14. ηrel may be indicated.

  In various embodiments, the oligomeric phosphonate may react with the epoxy. For example, a chemical reaction may take place between the phosphonate groups of the oligomeric phosphonate and the epoxy ring and secondary hydroxyl groups of the epoxy resin. This reaction occurs during the cure cycle (at temperatures> 150 ° C.) and produces a crosslinked epoxy system with a high glass transition temperature, typically above 160 ° C.

式中、Ａｒは、芳香族基であり、−Ｏ−Ａｒ−Ｏ−は、１以上の場合により置換されているアリール環を有するジヒドロキシ化合物、例えば、限定されないが、レゾルシノール、ヒドロキノン、ならびにビスフェノール、例えば、ビスフェノールＡ、ビスフェノールＦ、及び４，４’−ビフェノール、フェノールフタレイン、４，４’−チオジフェノール、４，４’−スルホニルジフェノール、３，３，５−トリメチルシクロヘキシルジフェノール、またはこれらの組み合わせに由来していてよく、Ｒは、Ｃ_１〜２０アルキル、Ｃ_２〜２０アルケン、Ｃ_２〜２０アルキン、Ｃ_５〜２０シクロアルキル、またはＣ_６〜２０アリールであり、ｎは、１〜約２０、１〜約１０、若しくは２〜約５の整数、またはこれらの範囲の間のあらゆる整数である；によって示される構造単位を含む。 Embodiments of the present invention are not limited by the type of oligophosphonate, colooligo (phosphonate ester), or colooligo (phosphonate carbonate); in certain embodiments, the oligophosphonate, colooligo (phosphonate ester), or colooligo (phosphonate) Carbonates are disclosed in U.S. Patent Nos. 6,861,499, 7,816,486, 7,645,850 and 7,838,604, each of which is incorporated herein by reference in its entirety. And the structure described and claimed in US Patent Application Publication No. 2009/0032770. Briefly, such oligomers may include repeating units derived from diarylalkylphosphonates or diarylarylphosphonates. For example, in some embodiments, such phosphonate oligomers have the formula I:

Wherein Ar is an aromatic group and -O-Ar-O- is a dihydroxy compound having one or more optionally substituted aryl rings, such as, but not limited to, resorcinol, hydroquinone, and bisphenol. For example, bisphenol A, bisphenol F, and 4,4'-biphenol, phenolphthalein, 4,4'-thiodiphenol, 4,4'-sulfonyldiphenol, 3,3,5-trimethylcyclohexyldiphenol, or Derived from these combinations, R is C _1-20 alkyl, C _2-20 alkene, C _2-20 alkyne, C _5-20 cycloalkyl, or C _6-20 aryl, and n is An integer from 1 to about 20, 1 to about 10, or 2 to about 5, or any integer between these ranges. ; Comprising structural units represented by the.

及びこれらの組み合わせ：式中、Ａｒ、Ａｒ^１、及びＡｒ^２は、それぞれ、独立して、芳香族基であり、−Ｏ−Ａｒ−Ｏ−は、１以上の場合により置換されているアリール環を有するジヒドロキシ化合物、例えば、限定されないが、レゾルシノール、ヒドロキノン、ならびにビスフェノール、例えば、ビスフェノールＡ、ビスフェノールＦ、及び４，４’−ビフェノール、フェノールフタレイン、４，４’−チオジフェノール、４，４’−スルホニルジフェノール、３，３，５−トリメチルシクロヘキシルジフェノール、またはこれらの組み合わせに由来していてよく、Ｒは、Ｃ_１〜２０アルキル、Ｃ_２〜２０アルケン、Ｃ_２〜２０アルキン、Ｃ_５〜２０シクロアルキル、またはＣ_６〜２０アリールであり、Ｒ^１及びＲ^２は、脂肪族または芳香族炭化水素であり、それぞれｍ、ｎ、及びｐは、同じまたは異なり得、独立して、１〜約２０、１〜約１０、若しくは２〜約５の整数、またはこれらの範囲の間のいずれの整数であることもできる；の構造を有していてよい。ある特定の実施形態において、それぞれｍ、ｎ、及びｐは、およそ５以上または１５未満である。 In other embodiments, the oligo (phosphonate carbonate) or oligo (phosphonate ester) has a structure, such as, but not limited to, Formula II and III, respectively:

And combinations thereof: wherein Ar, Ar ¹ , and Ar ² are each independently an aromatic group, and —O—Ar—O— is one or more optionally substituted aryl rings Dihydroxy compounds having, for example, but not limited to, resorcinol, hydroquinone, and bisphenols such as bisphenol A, bisphenol F, and 4,4′-biphenol, phenolphthalein, 4,4′-thiodiphenol, 4,4 '-Sulfonyldiphenol, 3,3,5-trimethylcyclohexyldiphenol, or a combination thereof, wherein R is _C1-20 alkyl, _C2-20 alkene, _C2-20 alkyne, C2 _5-20 cycloalkyl, or C _6-20 aryl, wherein R ¹ and R ² are aliphatic or An aromatic hydrocarbon, each m, n, and p can be the same or different and are independently an integer from 1 to about 20, 1 to about 10, or 2 to about 5, or between these ranges It can be any integer; In certain embodiments, each of m, n, and p is about 5 or more or less than 15.

  As indicated by the term "random", the monomers of the "random colooligo (phosphonate carbonate)" or "random colooligo (phosphonate ester)" of the various embodiments are randomly incorporated into the polymer chain, such that the oligomer The phosphonate chain may comprise alternating phosphonate and carbonate or ester monomers or short segments, wherein some phosphonate or carbonate or ester monomers are linked by an aromatic dihydroxide. The length of the segments may vary within individual random colooligo (phosphonate carbonate) or colooligo (phosphonate ester).

及びこれらの組み合わせ：式中、ｍ、ｎ、ｐ、ならびにＲ^１及びＲ^２は、それぞれ、上記のように定義されている；の構造を有していてよい。かかるコオリゴ（ホスホネートエステル）、またはコオリゴ（ホスホネートカーボネート）は、ブロックコオリゴ（ホスホネートエステル）、ブロックコオリゴ（ホスホネートカーボネート）であってよく、ここで、それぞれｍ、ｎ、及びｐは約１超であり、コポリマーは、別々の繰り返しホスホネート及びカーボネートブロックまたはホスホネート及びエステルブロックを含有する。他の実施形態において、オリゴマーコオリゴ（ホスホネートエステル）またはコオリゴ（ホスホネートカーボネート）は、ランダムコポリマーであり得、ここで、それぞれｍ、ｎ、及びｐは変動し得、１〜約２０、１〜約１０、または２〜約５の範囲の整数であってよく、ｍ、ｎ、及びｐの合計が、１〜約２０、１〜約１０、若しくは２〜約５の整数、またはこれらの範囲の間のあらゆる整数である。 In certain embodiments, Ar, Ar ¹ , and Ar ² can be bisphenol A, where R is a reactive end group, including random and block colooligos (phosphonate carbonates) and colooligos (phosphonate esters). It may be a methyl group that imparts an oligomeric phosphonate. Such compounds have structures, such as, but not limited to, Formulas IV, V, and IV:

And combinations thereof: wherein m, n, p, and R ¹ and R ² are each as defined above; Such a colooligo (phosphonate ester) or colooligo (phosphonate carbonate) may be a block colooligo (phosphonate ester), a block colooligo (phosphonate carbonate), where m, n, and p are each greater than about 1 Yes, the copolymer contains separate repeating phosphonate and carbonate blocks or phosphonate and ester blocks. In other embodiments, the oligomeric colooligo (phosphonate ester) or colooligo (phosphonate carbonate) can be a random copolymer, where m, n, and p can each vary, from 1 to about 20, 1 to about 10, or an integer ranging from 2 to about 5, wherein the sum of m, n, and p is an integer from 1 to about 20, 1 to about 10, or 2 to about 5, or between these ranges Is any integer of.

Particularly with respect to colooligo (phosphonate ester), colooligo (phosphonate carbonate), block colooligo (phosphonate ester), and block colooligo (phosphonate carbonate), it is not desired to be bound by theory, but oligomers containing a carbonate component are: Either the carbonate monomer, in which the carbonate is block or randomly arranged, may provide improved toughness over oligomers derived solely from the phosphonate. Such co-oligomers are also high glass transition temperature than the phosphonate oligomers, T _g, and it may provide good thermal stability.

  In certain embodiments, the colooligo (phosphonate carbonate) comprises at least 20 mole percent of a diarylalkylphosphonate or optionally substituted diarylalkylphosphonate, one or more diarylcarbonates, and one or more aromatic dihydroxides. And the mole percent of high purity diarylalkylphosphonate is based on the total amount of transesterification components, ie, all diarylalkylphosphonates and all diarylcarbonates. Similarly, certain embodiments of the oligo (phosphonate ester) comprise at least 20 mole% of diarylalkyl phosphonate or optionally substituted diarylalkylphosphonate, one or more diarylester, and one or more aromatic diarylalkylphosphonate. The mole percent of high purity diarylalkylphosphonate, which may be synthesized from the hydroxide, is based on the total amount of transesterification component.

  The phosphonate and carbonate content of the oligomeric phosphonate, random or block colooligo (phosphonate carbonate) and colooligo (phosphonate ester) may vary between embodiments, which may be phosphonate and / or carbonate content or phosphonate and / or Or, it is not limited by the range of the carbonate content. For example, in some embodiments, the colooligo (phosphonate carbonate) or colooligo (phosphonate ester) may have a phosphorus content of about 1% to about 12% by weight of the total oligomer, and in other embodiments, The phosphorus content may be from about 2% to about 10% by weight of the total oligomer.

  The hyperbranched oligomers of various embodiments have a highly branched structure and a high degree of functionality (ie, chemical reactivity). The branched structure of such a hyperbranched oligomer has a high concentration of terminal groups and reactive functional groups such as hydroxyl terminal groups, epoxy terminal groups, vinyl terminal groups, vinyl ester terminal groups, isopropenyl terminal groups, and isocyanate terminal groups. Create a terminal group at the end of every branch that may have. In some embodiments, hyperbranched oligomers may have a unique combination of chemical and physical properties when compared to linear oligomeric phosphonates. For example, a high degree of branching can prevent crystallization and reduce the possibility of chain entanglement, so that the hyperbranched oligomer has low solubility in organic solvents, and especially low solution when sheared. The viscosity and the melt viscosity can be shown.

  In some embodiments, the hyperbranched oligomer may contain branches that are not completely (ie, absolutely regular) arranged. For example, different branches in a single hyperbranched oligomer may have different lengths of the functional composition, and the like, and combinations thereof. As a result, in some embodiments, the hyperbranched oligomers of the present invention may have a broad molecular weight distribution. In other embodiments, the hyperbranched oligomers of the present invention may be completely branched, including branches that are substantially identical, and may have a monodisperse molecular weight distribution.

  The degree of branching of the hyperbranched oligomers of the present invention is defined as the number average ratio of branching groups per molecule, i.e., the ratio of terminal groups and branching monomer units to the total number of terminal groups, branching monomer units, and linear monomer units. obtain. For linear oligomers, the degree of branching, defined by the number average ratio of branching groups per molecule, is zero; for an ideal dendrimer, the degree of branching is one. Hyperbranched oligomers may have a degree of branching that is intermediate between the degree of branching of the linear oligomer and the degree of branching of the ideal dendrimer. For example, the degree of branching of the hyperbranched oligomer may be from about 0.05 to about 1, about 0.25 to about 0.75, or about 0.3 to about 0.6, and in certain embodiments, The hyperbranched oligomer may have a number average ratio of branching groups of about 0.5.

式中、Ｂは、超分岐オリゴマーであり、ｗは、分岐数であり、ｖは、ゼロではない整数であり、Ｌは、連結基であり、Ｆは、反応性基である；によって一般に表されてよい。 The hyperbranched oligomer of the present invention has the following structural formula VII:

Wherein B is a hyperbranched oligomer, w is the number of branches, v is a non-zero integer, L is a linking group, and F is a reactive group; May be.

The linking group (L) can be any site compatible with the chemistry of the oligophosphonate, colooligo (phosphonate ester), or colooligo (phosphonate carbonate) monomers described above. For example, in some embodiments, L can be any unit derived from an aryl or heteroaryl group, including a single aryl, biaryl, triaryl, tetraaryl, and the like. In other embodiments, L can be a covalent bond that links the functional group (F) directly to the hyperbranched oligomer; in yet other embodiments, L can be branched or unbranched C _1. -C _{10 alkyl,} may be C 2 _{-C 10} alkene or _C 2 _{-C 10} alkyne,.

  The linking group (L) allows the attachment of one or more functional groups (F) to each branch end of the hyperbranched oligomer. In some embodiments, each branch terminus may have a linked linking group, and in other embodiments, one or more branch ends of the hyperbranched oligomer (B) have a linked linking group. You don't have to. Such branch ends without an attached linking group may terminate at hydroxyl or phenol groups associated with the monomer units of the hyperbranched oligomer. At the branch terminus comprising the linking group (L), each linking group may have from 0 to 5 or more related functional groups. Thus, in some embodiments, one or more linking groups of a reactive hyperbranched oligomer may have no attached functional groups, such that the branch termination associated with the linking group is substantially Become non-reactive. In other embodiments, one or more linking groups of the reactive hyperbranched oligomer have one or more attached functional groups to terminate a branch end that is potentially reactive with another monomer, oligomer, or polymer. In still other embodiments, one or more linking groups of the reactive hyperbranched oligomer may have multiple attached functional groups. For example, two of the aryl groups involved in the triaryl group may include a third aryl group functional group (F) that attaches the linking group to the hyperbranched polymer or oligomer. The functional group (F) can vary between embodiments and can be any chemical moiety capable of reacting with another chemical moiety. Non-limiting examples of functional group (F) include hydroxyl, carboxylic acid, amine, cyanate, isocyanate, epoxy, glycidyl ether, vinyl, and the like, and combinations thereof. The reactive hyperbranched oligomers of the present invention are reactive with various functional groups, such as epoxies, anhydrides, activated halides, carboxylic acids, carboxylic esters, isocyanates, aldehydes, vinyls, acetylenes, and silanes. is there. These groups may be present on another monomer, oligomer, or polymer used to prepare the polymer composition.

式中、Ａｒは、芳香族基であり、−Ｏ−Ａｒ−Ｏ−は、１以上の場合により置換されているアリール環を有するジヒドロキシ化合物、例えば、限定されないが、レゾルシノール、ヒドロキノン、ならびにビスフェノール、例えば、ビスフェノールＡ、ビスフェノールＦ、及び４，４’−ビフェノール、フェノールフタレイン、４，４’−チオジフェノール、４，４’−スルホニルジフェノール、３，３，５−トリメチルシクロヘキシルジフェノール、またはこれらの組み合わせに由来していてよく、Ｒは、Ｃ_１〜２０アルキル、Ｃ_２〜２０アルケン、Ｃ_２〜２０アルキン、Ｃ_５〜２０シクロアルキル、またはＣ_６〜２０アリールを有する化合物に由来してよく、ｎは、１〜約２０、１〜約１０、若しくは２〜約５の整数、またはこれらの範囲の間のあらゆる整数である；の単位を含む構造を有していてよい。 The hyperbranched oligomer moiety (B) of the general structure presented above may be any phosphonate-containing hyperbranched oligomer. For example, in some embodiments, such hyperbranched oligomers may include recurring units derived from diarylalkyl- or diarylarylphosphonates, and in certain embodiments, such hyperbranched oligomers have formula I:

Wherein Ar is an aromatic group and -O-Ar-O- is a dihydroxy compound having one or more optionally substituted aryl rings, such as, but not limited to, resorcinol, hydroquinone, and bisphenol. For example, bisphenol A, bisphenol F, and 4,4'-biphenol, phenolphthalein, 4,4'-thiodiphenol, 4,4'-sulfonyldiphenol, 3,3,5-trimethylcyclohexyldiphenol, or may have derived from combinations thereof, R _{represents, C 1 to 20 alkyl,} derived from _{C 2 to 20 alkenes, C 2 to 20 alkyne, C 5 to 20} cycloalkyl or a compound having a _{C having 6 to 20} aryl, N may be an integer from 1 to about 20, 1 to about 10, or 2 to about 5, or a range thereof. It may have a structure comprising units of; is any integer between.

式中、それぞれＲ^３、Ｒ^４、及びＲ^５は、独立して、水素、Ｃ_１−Ｃ_４アルキルであり得、ｐ、ｑ、及びｒの各々は、独立して、１〜５の整数である；のリン酸トリアリールなどであってよい。 The hyperbranched oligomer (B) of such an embodiment may further include a unit derived from a branching agent, or a polyfunctional aryl, a polyfunctional biaryl group, a polyfunctional triaryl group, a polyfunctional tetraaryl, or the like. . In some embodiments, units derived from a branching agent may be derived, for example, from a polyfunctional acid, a polyfunctional glycol, or an acid / glycol hybrid. In other embodiments, the hyperbranched oligomeric phosphonate is a tri- or tetrahydroxy aromatic compound or a triaryl or tetraaryl phosphate, a triaryl or tetraaryl carbonate or a triaryl or tetraaryl ester or a combination thereof, such as a Although not included, it may have units derived from trimesic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride, trimethylolpropane, dimethylhydroxyl terephthalate, pentaerythritol, and the like, and combinations thereof. Such branching agents provide branch points within the hyperbranched oligomeric phosphonate. In certain embodiments, the branching agent is a triaryl phosphate, for example, Formula VIII:

Wherein each of R ³ , R ⁴ , and R ⁵ can independently be hydrogen, C ₁ -C ₄ alkyl, and each of p, q, and r is independently an integer from 1 to 5 A triaryl phosphate or the like.

  The number of branches (w) may be directly proportional to the number of units derived from the branching agent, and may be any integer from about 2 to about 20. In some embodiments, n can be greater than 3, greater than 5, or greater than 10, or any value within these ranges; in other embodiments, n is from about 5 to about 20, It can be about 5 to about 15, about 5 to about 10, or any value between these ranges.

式中、それぞれＡｒ^３及びＡｒ^４は、独立して、芳香族基であり、−Ｏ−Ａｒ^３−Ｏ−及び−Ｏ−Ａｒ^４−Ｏ−は、１以上の場合により置換されているアリール環を有するジヒドロキシ化合物、例えば、限定されないが、レゾルシノール、ヒドロキノン、ならびにビスフェノール、例えば、ビスフェノールＡ、ビスフェノールＦ、及び４，４’−ビフェノール、フェノールフタレイン、４，４’−チオジフェノール、４，４’−スルホニルジフェノール、３，３，５，−トリメチルシクロヘキシルジフェノールまたはこれらの組み合わせに由来することができ、各Ｌ^１及びＬ^２は、独立して、共有結合、または、単一のアリール基、ビアリール基、トリアリール基、テトラアリール基などを含めたアリール若しくはヘテロアリール基であり、Ｒは、Ｃ_１〜２０アルキル、Ｃ_２〜２０アルケン、Ｃ_２〜２０アルキン、Ｃ_５〜２０シクロアルキル、またはＣ_６〜２０アリールであり得、ｚは、１〜約２０、１〜約１０、若しくは２〜約５の整数、またはこれらの範囲の間のあらゆる整数であり、各ｗ^１及びｗ^２は、独立して、１〜５である；を有する構造を有していてよい。Ｘは、上記のいずれの分岐剤に由来していてもよい。いくつかの実施形態において、個々のＢにおけるＸは、同じ分子であってよく、その結果、式ＶＩＩ及び式ＶＩＩの構造を有する分岐が、同じ分岐剤（Ｘ）分子から延在していてよいようになる。特定の実施形態において、Ｘは、上記のように式ＶＩＩＩのリン酸トリアリールであってよい。他の実施形態において、２以上のＸは、式ＸＩ、式ＸＩＩ、または式ＸＩＩＩＩ：

式中、それぞれＢ^１及びＢ^２は、独立して、上記の超分岐ポリマーであり、各Ｘ^１及びＸ^２は、独立して、上記の分岐剤であり、各Ａｒ^５及びＡｒ^６は、独立して、芳香族基であり、−Ｏ−Ａｒ^５−Ｏ−及び−Ｏ−Ａｒ^６−Ｏ−は、１以上の場合により置換されているアリール環を有するジヒドロキシ化合物、例えば、限定されないが、レゾルシノール、ヒドロキノン、ならびにビスフェノール、例えば、ビスフェノールＡ、ビスフェノールＦ、及び４，４’−ビフェノール、フェノールフタレイン、４，４’−チオジフェノール、４，４’−スルホニルジフェノール、３，３，５−トリメチルシクロヘキシルジフェノールまたはこれらの組み合わせに由来することができ、各Ｒは上記の通りであり、ｓは、１〜約２０、１〜約１０、若しくは２〜約５の整数、またはこれらの間のあらゆる整数である；に示されるように連結されていてよい。種々の実施形態において、個々の反応性超分岐オリゴマーは、オリゴマーの部が式Ｉ、及びＶＩＩＩ〜ＸＩＩＩのいずれかであり得る構造を有していてよい。このように、実施形態は、上記で付与した式のいずれの組み合わせも有する反応性超分岐オリゴマーを包含する。他の実施形態において、反応性超分岐オリゴマーは、上記に提示した式の実質的に１または２の構造から構成されていてよい。例えば、超分岐オリゴマーは、式ＩＸの分岐を有する式ＸＩの構造によって連結されている分岐剤（Ｘ）に由来する２つの単位から構成されていてよく、または超分岐オリゴマーは、構造式ＩＸの分岐を有する式ＸＩ及びＸＩＩＩの構造によって連結されている３若しくは４の分岐剤から構成されていてよい。当然ながら、上記で議論されているように、式のいずれの組み合わせも可能であり、単一の反応性超分岐オリゴマーに存在し得る。 Certain embodiments of the reactive hyperbranched phosphonate are those wherein B is of the formula IX or X:

Wherein Ar ³ and Ar ⁴ are each independently an aromatic group, and —O—Ar ³ —O— and —O—Ar ⁴ —O— are one or more optionally substituted aryl Dihydroxy compounds having a ring, such as, but not limited to, resorcinol, hydroquinone, and bisphenols, such as bisphenol A, bisphenol F, and 4,4'-biphenol, phenolphthalein, 4,4'-thiodiphenol, 4,4 It can be derived from 4'-sulfonyldiphenol, 3,3,5, -trimethylcyclohexyldiphenol or a combination thereof, wherein each L ¹ and L ² is independently a covalent bond or a single aryl Or aryl or heteroaryl groups, including groups, biaryl groups, triaryl groups, tetraaryl groups, etc. R _{is C 1 to 20} alkyl _can be a _{C 2 to 20 alkenes, C 2 to 20 alkyne, C 5 to 20} cycloalkyl or _{C having 6 to 20} aryl,, z is 1 to about 20,1～ to about 10 Or an integer from 2 to about 5, or any integer between these ranges, wherein each w ¹ and w ² is independently 1-5. X may be derived from any of the above branching agents. In some embodiments, X in each B can be the same molecule, so that the branches having the structure of Formula VII and Formula VII can extend from the same branching agent (X) molecule. Become like In certain embodiments, X can be a triaryl phosphate of formula VIII as described above. In other embodiments, two or more Xs are of formula XI, XII, or XIIII:

Wherein each of B ¹ and B ² is independently a hyperbranched polymer as described above, each X ¹ and X ² is independently a branching agent as described above, and each Ar ⁵ and Ar ⁶ are independently, an aromatic group, ^-O-Ar 5 -O- and ^-O-Ar 6 -O- is dihydroxy compound having an aryl ring optionally substituted with one or more, for example, but not limited , Resorcinol, hydroquinone, and bisphenols such as bisphenol A, bisphenol F, and 4,4'-biphenol, phenolphthalein, 4,4'-thiodiphenol, 4,4'-sulfonyldiphenol, 3,3 5-trimethylcyclohexyldiphenol or a combination thereof, wherein each R is as described above and s is 1 to about 20, 1 to about 10, Or an integer from 2 to about 5, or any integer in between. In various embodiments, individual reactive hyperbranched oligomers can have a structure wherein the oligomer portion can be of Formula I and any of VIII-XIII. Thus, embodiments include reactive hyperbranched oligomers having any combination of the formulas given above. In other embodiments, the reactive hyperbranched oligomer may consist essentially of one or two structures of the formulas provided above. For example, a hyperbranched oligomer may be composed of two units derived from a branching agent (X) linked by a structure of Formula XI having a branch of Formula IX, or a hyperbranched oligomer of Formula IX It may be composed of 3 or 4 branching agents linked by a branched structure of formulas XI and XIII. Of course, as discussed above, any combination of the formulas is possible and may be present in a single reactive hyperbranched oligomer.

式中、Ａｒは、アリールまたはヘテロアリール基であり、Ｒは、Ｃ_１〜Ｃ_４アルキル基またはアリール基であり、Ｒ’は、分岐剤由来のアルキルまたは芳香族基である。 Illustrative representatives of the reactive hyperbranched oligomers of the present invention are provided below:

In the formula, Ar is an aryl or heteroaryl radical, R is a C ₁ -C ₄ alkyl group or an aryl group, R 'is an alkyl or aromatic group derived from a branching agent.

  The phosphonate and carbonate content of hyperbranched oligomeric phosphonates, random or block colooligos (phosphonate carbonates), and colooligos (phosphonate esters) may vary from embodiment to embodiment, with embodiments comprising phosphonate and / or carbonate content, Or it is not limited by the range of phosphonate and / or carbonate content. For example, in some embodiments, the colooligo (phosphonate carbonate) or colooligo (phosphonate ester) contains less than about 2% to about 12%, 2% to about 10%, or less than 10% by weight of the total oligomers of phosphorus. May have an amount.

  The reactive hyperbranched oligomer of various embodiments has more than about 40% or more than about 50% reactive end groups, based on the total number of branch terminations determined by known titration methods. In certain embodiments, the reactive hyperbranched oligomer may have more than about 75% or more than 90% reactive end groups, based on the total number of branch terminations determined by known titration methods. In a further embodiment, the reactive hyperbranched oligomer has from about 40% to about 98% reactive end groups, from about 50% to about 95% reactive end groups, or from about 60% to about 98%, based on the total number of branch terminations. It may have about 90% end groups. As discussed above, individual branch terminations may have more than one reactive end group. Thus, in some embodiments, the reactive hyperbranched oligomer may have more than 100% reactive end groups. As discussed above, the term "reactive end group" is used to describe any chemical site at a branch terminus that can react with another chemical site. Numerous reactive functional groups are known in the art and are encompassed by the present invention. In certain embodiments, a reactive end group can be a hydroxyl, epoxy, vinyl, or isocyanate group.

  Without wishing to be bound by theory, due to the hyperbranched nature, the reactive hyperbranched oligomers of the present invention exhibit lower melt viscosities when sheared compared to linear oligomeric phosphonates. Good. As such, the reactive hyperbranched oligomers described herein can be blended with monomers, oligomers, and polymers without reducing melt processability. The hyperbranched oligophosphonates of various embodiments may thus provide better meltability and improved processing. Also, the reactive hyperbranched oligomers of the present invention may have a higher molecular weight than similar compositions prepared using linear oligomeric phosphonates, increase the cross-linking of the polymer composition and increase its toughness. May be imparted to improve reactivity. In some embodiments, the reactive hyperbranched oligomers of the present invention may be used as a reactive or non-reactive additive in thermoplastics to improve shear thinning. For example, hyperbranched oligomers with or without reactive end groups that can be used to improve shear thinning without reacting or crosslinking the polymer to which the oligomer is added may be prepared.

The oligomeric phosphonates of various embodiments, including linear and hyperbranched oligophosphonates, can exhibit a high molecular weight and / or a narrow molecular weight distribution (ie, low polydispersity). For example, in some embodiments, the oligomeric phosphonate may have a weight average molecular weight (Mw) from about 1,000 g / mol to about 18,000 g / mol as determined by η _rel or GPC, and in other implementations. In an embodiment, the oligomeric phosphonate may have a Mw from about 1,000 to about 15,000 g / mol as determined by η _rel or GPC. The number average molecular weight (Mn), in such embodiments, can be from about 1,000 g / mol to about 10,000 g / mol, or from about 1,000 g / mol to about 5,000 g / mol, and in certain implementations. In embodiments, Mn may be greater than about 1,200 g / mol. The narrow molecular weight distribution (i.e., Mw / Mn) of such oligomeric phosphonates can be from about 1 to about 7 in some embodiments, and from about 1 to about 5 in other embodiments. In yet other embodiments, the oligo (phosphonate carbonate) may have a relative viscosity (η _rel ) of about 1.01 to about 1.20. Without wishing to be bound by theory, the relatively high molecular weight and narrow molecular weight distribution of the oligomeric phosphonates of the present invention may provide a superior combination of properties. For example, the oligomeric phosphonates of the embodiments are extremely flame retardant and exhibit excellent hydrolytic stability, and such properties are imparted to the polymer in combination with the oligomeric phosphonate to provide a polymer composition, for example, The described ones can be generated. Also, the oligomeric phosphonates of the embodiments generally exhibit an excellent combination of processing properties, including, for example, good thermal and mechanical properties.

  The concentration of the oligomeric phosphonate in the compositions of the various embodiments can vary, and any concentration that provides a suitable combination of glass transition temperature, heat resistance, and flame retardancy can be used. For example, in some embodiments, the composition may include from about 5% by weight (% by weight) to about 60% by weight. In other embodiments, the composition is encompassed by about 10% to about 50%, about 15% to about 45%, about 20% to about 40% by weight, or an exemplary range thereof. It may include any individual concentration or range of concentrations.

  The compositions of the various embodiments are not limited to any particular carbodiimide and any carbodiimide, or combinations of these carbodiimides can be incorporated into the compositions described above. Examples of useful carbodiimides include, but are not limited to, N, N'-di-2,6-diisopropylphenylcarbodiimide, N, N'-di-o-tolylcarbodiimide, N, N'-diphenylcarbodiimide, N, N ' -Dioctyldecylcarbodiimide, N, N'-di-2,6-dimethylphenylcarbodiimide, N-tolyl-N'-cyclohexylcarbodiimide, N, N'-di-2,6-di-tert-butylphenylcarbodiimide, N -Tolyl-N'-phenylcarbodiimide, N, N'-di-p-nitrophenylcarbodiimide, N, N'-di-p-aminophenylcarbodiimide, N, N'-di-p-hydroxyphenylcarbodiimide, N'-di-cyclohexylcarbodiimide, N, N'-di-p-tolylcarbodiimide p-phenylene-bis-di-o-tolylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, hexamethylene-bis-dicyclohexylcarbodiimide, 4,4′-dicyclohexylmethanecarbodiimide, ethylene-bis-diphenylcarbodiimide, N, N ′ -Benzylcarbodiimide, N-octadecyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-octadecyl-N'-tolylcarbodiimide, N-cyclohexyl-N'-tolylcarbodiimide, N-phenyl-N ' -Tolylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, N, N'-di-o-ethylphenylcarbodiimide, N, N'-di-p-ethylphenylcarbodiimide, N, N'-di- -Isopropylphenylcarbodiimide, N, N'-di-p-isopropylphenylcarbodiimide, N, N'-di-o-isobutylphenylcarbodiimide, N, N'-di-p-isobutylphenylcarbodiimide, N, N'-di -2,6-diethylphenylcarbodiimide, N, N'-di-2-ethyl-6-isopropylphenylcarbodiimide, N, N'-di-2-isobutyl-6-isopropylphenylcarbodiimide, N, N'-di- 2,4,6-trimethylphenylcarbodiimide, N, N'-di-2,4,6-triisopropylphenylcarbodiimide, N, N'-di-2,4,6-triisobutylphenylcarbodiimide, diisopropylcarbodiimide, dimethyl Carbodiimide, diisobutyl carbodiimide, dioctyl Examples include rucarbodiimide, t-butylisopropylcarbodiimide, di-β-naphthylcarbodiimide, di-t-butylcarbodiimide, and aromatic polycarbodiimide, and polymers of these compounds. In certain embodiments, the carbodiimide is an aromatic carbodiimide, for example, N, N'-di-2,6-diisopropylphenylcarbodiimide, or a carbodiimide having one or more cyclo rings, for example, 4,4'-. It may be dicyclohexylmethanecarbodiimide or a polymer of these compounds. In certain embodiments, the carbodiimide is N, N′-dicyclohexylcarbodiimide, N-cyclohexyl-N ′-(2-morpholinoethyl) carbodiimide meth-p-toluenesulfonate, bis (trimethylsilyl) carbodiimide, N- (3-dimethyl Aminopropyl) -N'-ethylcarbodiimide, N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide hydrochloride, 1,3-di-p-tolylcarbodiimide, N, N'-bis (2-methylphenyl ) Carbodiimide, N- (tert-butyl) -N ′-[1- (2-chlorophenyl) -1-methylethyl] carbodiimide, N- (tert-butyl) -N ′-(2,6-dichlorophenyl) carbodiimide, N-butyl-N '-[1- (2-chlorophenyl) -1 Methylethyl] carbodiimide, N, N'-diisopropylcarbodiimide, dicyclohexylcarbodiimide, may be N- benzyl -N'- cyclohexyl carbodiimide.

  The concentration of the carbodiimide in the compositions of the various embodiments may vary, and any concentration that provides a suitable combination of glass transition temperature, heat resistance, and flame retardancy may be used. For example, in some embodiments, the composition may include from about 0.01% by weight (% by weight) to about 4.0% by weight. In other embodiments, the composition comprises from about 0.05% to about 3%, from about 0.1% to about 2%, from about 0.5% to about 1.0% by weight, Or any individual concentration or range of concentrations encompassed by these exemplary ranges.

The phenolic antioxidant and phosphite antioxidant in the above composition include, for example, sterically hindered phenolic antioxidant, hydrolysis-stable organic phosphite, organic phosphite antioxidant, sterically hindered lactone antioxidant Any of the phenolic antioxidants and phosphite antioxidants known in the art, including agents and the like, may be phenolic antioxidants, phosphite antioxidants, or combinations thereof. Sterically hindered phenolic antioxidants, organic phosphite antioxidants, hydrolytically stable organic phosphites and sterically hindered lactones and amine antioxidants are a broad class of additions that can encompass many similar chemical structures Represents an agent. Table 1 gives specific examples of such antioxidants.

  In certain embodiments, the antioxidant is a hindered phenol, for example, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-. Diylbis (3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)), 3,3 ′, 3 ′, 5,5 ′, 5′-hexa-tert-butyl-a, a ′ , A '-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, and the like. In some embodiments, the antioxidant is a phosphite antioxidant, for example, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, tris (2,4-ditert-butylphenyl). It may be phosphite or the like. In certain embodiments, the antioxidant may be a combination of these hindered phenol and phosphite antioxidants.

  The concentrations of the phenolic antioxidant and the phosphite antioxidant in the compositions of the various embodiments may vary, and any concentration that provides a suitable combination of glass transition temperature, heat resistance, and flame retardancy is used. You can also. For example, in some embodiments, the composition can include from about 0.01% to about 1.0% by weight. In other embodiments, the composition is encompassed by about 0.05% to about 0.75% by weight, about 0.1% to about 0.5% by weight, or an exemplary range thereof. Any individual concentration or range of concentrations may be included.

  In such embodiments, any epoxy resin can be used, and in certain embodiments, the resin is a diglycidyl capable of reacting with the epoxy groups associated with the epoxy-containing phosphonate polymers, copolymers, oligomers and cooligomers of the present invention. Groups, alicyclic epoxy groups, oxirane groups, ethoxylin groups, or similar epoxy groups or combinations thereof. Such epoxy resins are well known in the art and include, but are not limited to, novolak type epoxy resins, cresol-novolak epoxy resins, triphenol alkane type epoxy resins, aralkyl type epoxy resins, aralkyl type epoxy resins having a biphenyl skeleton, biphenyl type. Epoxy resin, dicyclopentadiene type epoxy resin, heterocyclic type epoxy resin, epoxy resin containing naphthalene ring, bisphenol A type epoxy compound, bisphenol F type epoxy compound, stilbene type epoxy resin, trimethylol-propane type epoxy resin, terpene Modified epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, or sulfur-containing epoxy resin obtained by oxidizing olefin bond with peracetic acid or similar peracid It is below. In some embodiments, the epoxy resin may be comprised of two or more epoxy resins of any of the above types. In certain embodiments, the epoxy resin may be an aralkyl-type epoxy resin, for example, an epoxy resin derived from bisphenol A or 4,4'-methylenedianiline. The epoxy may contain one or more additional components, such as, for example, a benzoxazine compound or resin, and in some embodiments, the novel epoxy-containing phosphonate monomers, polymers, copolymers, oligomers and cooligomers are: It may be used as an epoxy modifier, a chain extender or crosslinker for epoxy resins, or an epoxy curing agent in such epoxy resin polymer compositions.

  The compositions described above may comprise additional ingredients, such as additives, fillers, and fibers, such as, but not limited to, chopped or continuous glass fibers, metal fibers, aramid fibers, carbon fibers, or ceramic fibers, surfactants, organics. Binders, polymer binders, crosslinking agents, diluents, coupling agents, flame retardants, anti-dripping agents, for example, fluorinated polyolefins, silicones, and lubricants, mold release agents, for example, pentaerythritol tetrastearate, Nucleating agents, antistatic agents, such as conductive black, carbon nanotubes, graphite, graphene, graphene oxide, and organic antistatic agents, such as polyalkylene ethers, alkyl sulfonates, perfluorosulfonic acid, perfluorobutane, sulfonic acid Potassium salt, polyamide-containing polymer, catalyst, Agents, inks, dyes, antioxidants, stabilizers, etc., as well as may contain combinations of any of these.

  In such embodiments, each of the additional components or additives comprises from about 0.001% to about 1%, from about 0.005% to about 0.9%, about 0.005% by weight of the total composition. From about 0.04% to about 0.8% by weight, or from about 0.04% to about 0.8% by weight; in certain embodiments, the additional components or additives are about 0% by weight, based on the total composition. 0.04% to about 0.6% by weight. Further components, such as glass fibers, carbon fibers, organic fibers, ceramic fibers or other fillers, may be applied in high concentrations up to 70% (vol)%. For example, certain embodiments of the polymer composition comprise about 5% to about 70%, about 10% to about 60%, or about 20% to about 50% by volume of glass fibers, carbon fibers, Organic fibers or ceramic fibers may be included.

  Polymer compositions containing the novel epoxy-containing phosphonate monomers, polymers, copolymers, oligomers and cooligomers, and other engineering polymers and / or additional components or additives can be prepared by conventional means. For example, in some embodiments, the composition may be prepared by curing a liquid epoxy. Such embodiments may include combining an epoxy resin, an oligomeric phosphonate, and a carbodiimide antioxidant, or a combination of a carbodiimide and a phenolic or phosphite antioxidant in a solvent, in certain embodiments. The method may include combining the epoxy resin, oligomeric phosphonate, carbodiimide antioxidant, or combination of carbodiimide and phenolic or phosphite antioxidant, and the curing catalyst in a solvent. Combining may be performed by any means, including, for example, stirring or shaking the components until a substantially homogeneous mixture of components is created. In certain embodiments, the method comprises combining an epoxy resin, an oligomeric phosphonate, and a carbodiimide antioxidant, or a combination of a carbodiimide and a phenolic or phosphite antioxidant to form a mixture, and a solvent or It may include adding a solvent and a curing agent to the mixture. This mixture may be mixed by stirring or shaking.

  The form of addition of the compounds according to the invention is not limited. For example, the engineering plastic and / or further components or additives may be added as a solid, for example as a powder, as a concentrate in a solution, or as a liquid.

  The solvent of such embodiments can be any solvent known in the art, and in certain embodiments, the solvent can be an aprotic solvent. Examples of the aprotic solvent include, but are not limited to, perfluorohexane, a, a, a-trifluorotoluene, pentane, hexane, cyclohexane, methylcyclohexane, decalin [c + t], dioxane, carbon tetrachloride, Freon-11, benzene, Toluene, triethylamine, carbon disulfide, diisopropyl ether, diethyl ether (ether), t-butyl methyl ether (MTBE), chloroform, ethyl acetate, 1,2-dimethoxyethane (glyme), 2-methoxyethyl ether (diglyme), Tetrahydrofuran (THF), methylene chloride, pyridine (Py), methyl ethyl ketone (MEK), methyl n-amyl ketone (MAK), methyl n-propyl ketone (MPK), acetone, hexamethylphosphoramide, N- Chirupirorijinon, nitromethane, dimethylformamide, may be mentioned acetonitrile, sulfolane, dimethyl sulfoxide, and propylene carbonate. In certain embodiments, the solvent may be methyl ethyl ketone (MEK) or acetone.

  The amount of solvent included in the mixture of various embodiments can be from about 25% to about 75% by weight of the total composition, and in certain embodiments, the solvent is about 30% by weight of the total composition. To about 50% by weight, or any concentration or range encompassed by these exemplary ranges.

  Any curing agent and curing catalyst known in the art, such as, but not limited to, transition metal catalysts, tertiary amines, imidazole-containing compounds, and the like, and combinations thereof. Examples of the tertiary amine curing catalyst include triethylamine, benzyldimethylamine, pyridine, picoline, 1,8-diazabiscyclo (5,4,0) undecene-1, dicyandiamide, and the like, but are not limited to examples of imidazole compounds. But 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and the like.

  The amount of cure catalyst can be any amount that is effective for use as a catalyst, and can generally be from about 0.01% to about 20% by weight, based on the weight of the total composition. In some embodiments, the amount of curing catalyst is from about 0.1% to about 15%, from about 0.5% to about 10%, from about 1.0% to about 5%, or Any range or individual concentration encompassed by these exemplary ranges may be used.

  The method may further include heating the mixture after mixing the mixture to form a substantially uniform mixture to remove the solvent and produce a cured composition. Heating may be performed at any temperature suitable to allow good catalytic activity and evaporation of the solvent. In various embodiments, the heating is performed at about 20 ° C. to about 250 ° C., about 50 ° C. to about 200 ° C., about 100 ° C. to about 150 ° C., or any range or individual temperature encompassed by these ranges. May be. In certain embodiments, heating may be performed in more than one step. For example, the first heating step includes heating the mixture to a temperature suitable for evaporating the solvent, such as about 40 ° C. to about 150 ° C. or about 50 ° C. to about 100 ° C. for a first time period. Frequently, the second step may include heating the mixture to a temperature suitable for curing the mixture, for example, from about 100C to about 250C or from about 150C to about 200C. The time period for heating may vary between embodiments and may vary depending on the type of solvent used. Typically, heating may be performed for about 60 minutes to about 300 minutes, or for any range or individual period encompassed by the range. In embodiments where heating is performed for the first and second time periods, the first heating step may be performed for about 10 minutes to about 60 minutes, about 20 minutes to about 40 minutes, or about 30 minutes, The heating step may be performed for about 40 minutes to about 200 minutes or about 60 minutes to about 180 minutes, or any range or individual period encompassed by the range.

  The polymer compositions of the various embodiments can be used in any application where a flame retardant polymer is useful. For example, in some embodiments, the polymer compositions of the present invention can be used, for example, as fibers, woven mats, non-woven mats, fabrics, broadgoods, wovens, moldings, laminates, foams, extruded shapes, and the like. It may be used as a coating on plastic, metal, glass, carbon, ceramic, or wood products, which may be in various forms; in other embodiments, the polymer compositions of the present invention may be used in adhesives or in sheets, multilayer sheets , Free standing films, multilayer films, fibers, foams, molded articles, and fiber reinforced composites. Such articles may be suitable for applications requiring flame resistance. The novel epoxy-containing phosphonate monomers, polymers, copolymers, oligomers and co-oligomers and polymers therefrom, and the polymer compositions of the present invention exhibit very good flame resistance and good melt processability, making these materials exceptionally good. It may be useful in automotive, building, and electronic sector applications that require flame retardancy, high temperature performance, and melt processability. In addition, these articles may be used to support components, electrical components, electrical connectors, printed wiring boards, flexible or rigid circuit boards in consumer products that must meet UL or other standardized fire and environmental standards. , Electrical or electromagnetic housings, electrical or electromagnetic sub-components and components may be suitable for various applications.

  In some embodiments, the polymer compositions of the present invention may be combined with other components or reinforcing materials. For example, in various embodiments, continuous or chopped glass fibers, carbon black or carbon fibers, ceramic particles or fibers, organic fibers, or other organic materials may be included in the polymers and polymer compositions of the present invention. In certain embodiments, continuous or chopped glass fibers, carbon fibers, ceramic fibers, organic fibers, or other organic materials are used as the novel epoxy-containing phosphonate monomers, polymers, copolymers, oligomers and cooligomers therefrom, and the present invention. The prepreg may be combined with the inventive polymer composition to create a laminate. Such laminates are incorporated into articles of manufacture, such as appliances, such as televisions, computers, laptop computers, tablet computers, printers, mobile phones, video games, DVD players, stereos and other household appliances. The resulting component may be used to produce a flexible or rigid laminated circuit board, for example.

  The polymer compositions of the present invention are generally self-extinguishing, that is, they stop burning when removed from the flame, and any droplets produced by melting in the flame that stopped burning are extinguished almost instantaneously. Does not readily propagate the flame to any surrounding material. Furthermore, these polymer compositions do not develop noticeable smoke when a flame is applied.

  Although the invention has been described in considerable detail with reference to certain preferred embodiments thereof, other versions are possible. Therefore, the spirit and scope of the appended claims should not be limited to the detailed description and the preferred versions contained herein. Various aspects of the invention are illustrated by reference to the following non-limiting examples. The following examples are for illustrative purposes only and should not be construed as limiting the invention in any way.

Materials Two hydroxyl-terminated alkylphosphonate oligomer (FRX Polymer ^{(registered trademark)} Inc., Ltd. Nofia ^(TM) OL1001 and Nofia ^(TM) OL3001) and cresol novolac epoxy resin (Momentive made Epon164, epoxide equivalent: 200~240g / Equivalent).

2-Ethyl-4-methylimidazole and dicyandiamide were purchased from Sigma-Aldrich. Alkylphenyl carbodiimide and polymer type was purchased from RheinChemie (Stabaxol ^(R) 1 and Stabaxol ^(R) P). Pentaerythritol tetrakis [3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate], bis (2.4-di-t-butylphenyl) pentaerythritol diphosphite, and tris ( 2,4-Ditert-butylphenyl) phosphite was purchased from Sigma-Aldrich.

Methods GPC: The molecular weight distribution was determined by measuring a 0.2% solution of the polymer in tetrahydrofuran by gel permeation chromatography (GPC) with UV detection (at 254 nm). Instrument calibration was performed with linear polystyrene (PS) standards of known molecular weight. The weight average (Mw), number average (Mn) and polydispersity (Mw / Mn) (referred to as PD) were evaluated from the chromatogram by using WinGPC.

  DSC: glass transition temperature (Tg), drying cycle: 1) ramp at 10 ° C / min to 130 ° C, 2) equilibrate at 130 ° C, 3) quench to 0 ° C, 4) equilibrate at 0 ° C, and test cycle. : 5) ramp to 10O 0 C / min up to 250 0 C, 6) End of test: according to TA Instrument Q20.

Comparative Example 1
64 parts by weight of cresol novolak epoxy resin (Epon 164 manufactured by Momentive, epoxide equivalent: 200 to 240 g / equivalent), 36 parts by weight of hydroxyl-terminated alkyl phosphonate oligomer (Nofia OL1001 manufactured by FRX Polymer, molecular weight (Mn): 1,500 g / mol) , And 0.2 parts by weight of a 2-ethyl-4-methylimidazole solution (10% in methyl ethyl ketone) are mixed together, then the mixture is dissolved in 60 parts by weight of methyl ethyl ketone, followed by 60 parts by using a shaker. Mix for minutes. The epoxy formulation was poured into the mold and the solvent was allowed to evaporate at 130 ° C. for 30 minutes, then cured at 190 ° C. every 60 minutes for a maximum of 180 minutes. The glass transition temperature (Tg) of the cured epoxy resin was measured by using Differential Scanning Calorimetry (DSC) using TA Instrument Q20.

Comparative Example 2
64 parts by weight of cresol novolak epoxy resin (Epon 164 manufactured by Momentive, epoxide equivalent: 200 to 240 g / equivalent), 36 parts by weight of hydroxyl-terminated alkyl phosphonate oligomer (Nofia OL1001 manufactured by FRX Polymer, molecular weight (Mn): 1,500 g / mol) , 0.2 parts by weight of a 2-ethyl-4-methylimidazole solution (10% in methyl ethyl ketone) and 4 parts by weight of dicyandiamide are mixed together, then the mixture is dissolved in 60 parts by weight of methyl ethyl ketone, The mixture was mixed for 60 minutes using a shaker. The epoxy formulation was poured into the mold and the solvent was allowed to evaporate at 130 ° C. for 30 minutes, then cured at 190 ° C. every 60 minutes for a maximum of 180 minutes. The glass transition temperature (Tg) of the cured epoxy resin was measured by using Differential Scanning Calorimetry (DSC) using TA Instrument Q20.

Example 1
64 parts by weight of cresol novolak epoxy resin (Epon 164 manufactured by Momentive, epoxide equivalent: 200 to 240 g / equivalent), 36 parts by weight of hydroxyl-terminated alkyl phosphonate oligomer (Nofia OL1001 manufactured by FRX Polymer, molecular weight (Mn): 1,500 g / mol) , 0.2 part by weight of 2-ethyl-4-methylimidazole solution (10% in methyl ethyl ketone), and of 1.0 parts Stabaxol mixed ^(TM) 1 together and then a mixture of 60 parts by weight Dissolved in methyl ethyl ketone followed by mixing on a shaker for 60 minutes. The epoxy formulation was poured into the mold and the solvent was allowed to evaporate at 130 ° C. for 30 minutes, then cured at 190 ° C. every 60 minutes for a maximum of 180 minutes. The glass transition temperature (Tg) of the cured epoxy resin was measured by using Differential Scanning Calorimetry (DSC) using TA Instrument Q20.

Example 2
The same composition as in Example 1 was prepared, the solution was poured into a mold and dried, followed by curing at 200 ° C. for 60 minutes and 120 minutes, respectively. The glass transition temperature (Tg) of the cured epoxy resin was measured using a differential scanning calorimeter (DSC).

Example 3
64 parts by weight of cresol novolak epoxy resin (Epon 164 manufactured by Momentive, epoxide equivalent: 200 to 240 g / equivalent), 36 parts by weight of hydroxyl-terminated alkyl phosphonate oligomer (Nofia OL1001 manufactured by FRX Polymer, molecular weight (Mn): 1,500 g / mol) , 0.2 part by weight of 2-ethyl-4-methylimidazole solution (10% in methyl ethyl ketone), and of 2.0 parts Stabaxol mixed ^(TM) 1 together and then a mixture of 60 parts by weight Dissolved in methyl ethyl ketone followed by mixing on a shaker for 60 minutes. The epoxy formulation was poured into the mold and the solvent was allowed to evaporate at 130 ° C. for 30 minutes, then cured at 190 ° C. every 60 minutes for a maximum of 180 minutes. The glass transition temperature (Tg) of the cured epoxy resin was measured by using Differential Scanning Calorimetry (DSC) using TA Instrument Q20.

Example 4
The same composition as in Example 3 was prepared, the solution was poured into a mold and dried, followed by curing at 200 ° C. for 60 and 120 minutes, respectively. The glass transition temperature (Tg) of the cured epoxy resin was measured using a differential scanning calorimeter (DSC).

Example 5
64 parts by weight of cresol novolak epoxy resin (Epon 164 manufactured by Momentive, epoxide equivalent: 200 to 240 g / equivalent), 36 parts by weight of hydroxyl-terminated alkyl phosphonate oligomer (Nofia OL1001 manufactured by FRX Polymer, molecular weight (Mn): 1,500 g / mol) 0.2 parts by weight of a solution of 2-ethyl-4-methylimidazole (10% in methyl ethyl ketone), and 1.0 part by weight of pentaerythritol tetrakis [3- (3 ', 5'-di-tert-butyl-4). '-Hydroxyphenyl) propionate] and 0.5 parts by weight of bis (2.4-di-t-butylphenyl) pentaerythritol diphosphite are then mixed together, and the mixture is dissolved in 60 parts by weight of methyl ethyl ketone. And then the shaker It was mixed for 60 minutes using. The epoxy formulation was poured into the mold and the solvent was evaporated at 130 ° C. for 30 minutes, then cured at 200 ° C. for 60 and 120 minutes. The glass transition temperature (Tg) of the cured epoxy resin was measured by using Differential Scanning Calorimetry (DSC) using TA Instrument Q20.

Example 6
64 parts by weight of cresol novolak epoxy resin (Epon 164 manufactured by Momentive, epoxide equivalent: 200 to 240 g / equivalent), 36 parts by weight of hydroxyl-terminated alkyl phosphonate oligomer (Nofia OL1001 manufactured by FRX Polymer, molecular weight (Mn): 1,500 g / mol) , 0.2 part by weight of 2-ethyl-4-methylimidazole solution (10% in methyl ethyl ketone), and 1.0 part by weight of Stabaxol ^(R) 1, 1.0 parts by weight of pentaerythritol tetrakis [3- ( 3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] and 0.5 parts by weight of bis (2.4-di-t-butylphenyl) pentaerythritol diphosphite And then add 60 parts by weight of the mixture. In methyl ethyl ketone, followed by mixing on a shaker for 60 minutes. The epoxy formulation was poured into the mold and the solvent was evaporated at 130 ° C. for 30 minutes, then cured at 200 ° C. for 60 and 120 minutes. The glass transition temperature (Tg) of the cured epoxy resin was measured by using Differential Scanning Calorimetry (DSC) using TA Instrument Q20.

Example 7
64 parts by weight of cresol novolak epoxy resin (Epon 164 manufactured by Momentive, epoxide equivalent: 200 to 240 g / equivalent), 36 parts by weight of hydroxyl-terminated alkyl phosphonate oligomer (Nofia OL1001 manufactured by FRX Polymer, molecular weight (Mn): 1,500 g / mol) , 0.2 parts by weight of a 2-ethyl-4-methylimidazole solution (10% in methyl ethyl ketone) and 1.5 parts by weight of tris (2,4-ditert-butylphenyl) phosphite are mixed together, The mixture was then dissolved in 60 parts by weight of methyl ethyl ketone and subsequently mixed for 60 minutes using a shaker. The epoxy formulation was poured into the mold and the solvent was evaporated at 130 ° C. for 30 minutes, then cured at 200 ° C. for 60 and 120 minutes. The glass transition temperature (Tg) of the cured epoxy resin was measured by using Differential Scanning Calorimetry (DSC) using TA Instrument Q20.

Comparative Example 3
64 parts by weight of cresol novolak epoxy resin (Epon 164 from Momentive), 36 parts by weight of hydroxyl-terminated alkyl phosphonate oligomer (Nofia OL3001, from FRX Polymer, molecular weight (Mn): 2,700 g / mol), and 0.2 part by weight of 2 -Ethyl-4-methylimidazole solution (10% in methyl ethyl ketone) was mixed together, then the mixture was dissolved in 60 parts by weight of methyl ethyl ketone, followed by mixing on a shaker for 60 minutes. The epoxy formulation was poured into the mold and the solvent was evaporated at 130 ° C. for 30 minutes, then cured at 200 ° C. for 60 and 120 minutes. The glass transition temperature (Tg) of the cured epoxy resin was measured by using Differential Scanning Calorimetry (DSC) using TA Instrument Q20.

Example 8
64 parts by weight of a cresol novolak epoxy resin (Epon 164 manufactured by Momentive, epoxide equivalent: 200 to 240 g / equivalent), 36 parts by weight of a hydroxyl-terminated alkyl phosphonate oligomer (Nofia OL3001 manufactured by FRX Polymer, molecular weight (Mn): 2,700 g / mol) , 0.2 part by weight of 2-ethyl-4-methylimidazole solution (10% in methyl ethyl ketone), and of 2.0 parts Stabaxol mixed ^(TM) 1 together and then a mixture of 60 parts by weight Dissolved in methyl ethyl ketone followed by mixing on a shaker for 60 minutes. The epoxy formulation was poured into the mold and the solvent was evaporated at 130 ° C. for 30 minutes, then cured at 200 ° C. for 60 and 120 minutes. The glass transition temperature (Tg) of the cured epoxy resin was measured by using Differential Scanning Calorimetry (DSC) using TA Instrument Q20.

Example 9
64 parts by weight of a cresol novolak epoxy resin (Epon 164 manufactured by Momentive, epoxide equivalent: 200 to 240 g / equivalent), 36 parts by weight of a hydroxyl-terminated alkyl phosphonate oligomer (Nofia OL3001 manufactured by FRX Polymer, molecular weight (Mn): 2,700 g / mol) , 0.2 part by weight of 2-ethyl-4-methylimidazole solution (10% in methyl ethyl ketone), and of 2.0 parts Stabaxol mixed ^{(registered trademark)} P together and then a mixture of 60 parts by weight Dissolved in methyl ethyl ketone followed by mixing on a shaker for 60 minutes. The epoxy formulation was poured into the mold and the solvent was evaporated at 130 ° C. for 30 minutes, then cured at 200 ° C. for 60 and 120 minutes. The glass transition temperature (Tg) of the cured epoxy resin was measured by using Differential Scanning Calorimetry (DSC) using TA Instrument Q20.

Example 10
64 parts by weight of cresol novolak epoxy resin (Epon 164 manufactured by Momentive, epoxide equivalent: 200 to 240 g / equivalent), 36 parts by weight of hydroxyl-terminated alkyl phosphonate oligomer (Nofia OL3001 manufactured by FRX Polymer, molecular weight (Mn): 2,700 g / mol) , 0.2 part by weight of 2-ethyl-4-methylimidazole solution (10% in methyl ethyl ketone), and 1.0 part by weight of Stabaxol ^(R) 1 and 1.0 part by weight of tris (2,4-di (tert-Butylphenyl) phosphite was mixed together, and then the mixture was dissolved in 60 parts by weight of methyl ethyl ketone, followed by mixing for 60 minutes using a shaker. The epoxy formulation was poured into the mold and the solvent was evaporated at 130 ° C. for 30 minutes, then cured at 200 ° C. for 60 and 120 minutes. The glass transition temperature (Tg) of the cured epoxy resin was measured by using Differential Scanning Calorimetry (DSC) using TA Instrument Q20.

Example 11
64 parts by weight of a cresol novolak epoxy resin (Epon 164 manufactured by Momentive, epoxide equivalent: 200 to 240 g / equivalent), 36 parts by weight of a hydroxyl-terminated alkyl phosphonate oligomer (Nofia OL3001 manufactured by FRX Polymer, molecular weight (Mn): 2,700 g / mol) , 0.2 part by weight of 2-ethyl-4-methylimidazole solution (10% in methyl ethyl ketone), and 1.0 part by weight of Stabaxol ^(R) P and 1.0 part by weight of tris (2,4-di (tert-Butylphenyl) phosphite was mixed together, and then the mixture was dissolved in 60 parts by weight of methyl ethyl ketone, followed by mixing for 60 minutes using a shaker. The epoxy formulation was poured into the mold and the solvent was evaporated at 130 ° C. for 30 minutes, then cured at 200 ° C. for 60 and 120 minutes. The glass transition temperature (Tg) of the cured epoxy resin was measured by using Differential Scanning Calorimetry (DSC) using TA Instrument Q20.

Example 12
64 parts by weight of cresol novolak epoxy resin (Epon 164 manufactured by Momentive, epoxide equivalent: 200 to 240 g / equivalent), 36 parts by weight of hydroxyl-terminated alkyl phosphonate oligomer (Nofia OL3001 manufactured by FRX Polymer, molecular weight (Mn): 2,700 g / mol) , 0.2 parts by weight of a solution of 2-ethyl-4-methylimidazole (10% in methyl ethyl ketone) and 2.0 parts by weight of tris (2,4-ditert-butylphenyl) phosphite are mixed together, The mixture was then dissolved in 60 parts by weight of methyl ethyl ketone and subsequently mixed for 60 minutes using a shaker. The epoxy formulation was poured into the mold and the solvent was evaporated at 130 ° C. for 30 minutes, then cured at 200 ° C. for 60 and 120 minutes. The glass transition temperature (Tg) of the cured epoxy resin was measured by using Differential Scanning Calorimetry (DSC) using TA Instrument Q20.

Comparative Examples The components and DSC analysis of each of Comparative Examples 1 to 7 are given in Table 2:

The components and DSC analysis of each of Comparative Examples 3 to 12 are given in Table 3:

Claims (25)

Epoxy resin,
One or more oligomeric phosphonates;
About 0.01% to about 4.0% by weight of one or more carbodiimides.   The epoxy resin is novolak type epoxy resin, cresol-novolak epoxy resin, triphenol alkane type epoxy resin, aralkyl type epoxy resin, aralkyl type epoxy resin having a biphenyl skeleton, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, complex Ring type epoxy resin, epoxy resin containing naphthalene ring, bisphenol A type epoxy compound, bisphenol F type epoxy compound, stilbene type epoxy resin, trimethylol-propane type epoxy resin, terpene modified epoxy resin, peracetic acid or similar olefin bond Linear aliphatic epoxy resin obtained by oxidizing with a peracid, an alicyclic epoxy resin, a sulfur-containing epoxy resin, a phenol novolak type epoxy-containing benzoxazine, for example, Scan phenol A based benzoxazine, bisphenol F type benzoxazine, dicyclopentadiene-based benzoxazine, phenolphthalein-based benzoxazine, polyphenol type A benzoxazine, and is selected from the group consisting of The composition of claim 1.   The composition of claim 1, wherein the one or more oligomeric phosphonates are selected from the group consisting of linear oligomeric phosphonates, branched oligomeric phosphonates, and hyperbranched oligomeric phosphonates.   2. The composition of claim 1, wherein the one or more oligomeric phosphonates comprise from about 60% to about 100%, based on total terminal numbers, of reactive end groups.   The composition of claim 1, wherein the one or more oligomeric phosphonates are random or block colooligo (phosphonate ester) or random or block colooligo (phosphonate carbonate).   2. The method of claim 1, wherein the one or more oligomeric phosphonates comprise a reactive end group selected from the group consisting of hydroxyl, carboxylic acid, epoxy, glycidyl ether, vinyl, vinyl ester, isopropenyl, isocyanate, and combinations thereof. A composition according to claim 1.   The composition of claim 1, wherein the one or more oligomeric phosphonates have a reactive end group that is hydroxyl. The one or more oligomeric phosphonates are compounds of the formula (I):

Wherein R is a C1-C20 alkyl or an optionally substituted aryl group, X is an aromatic, cycloalkyl, or aliphatic group, and n is an integer from 1 to about 10 The composition of claim 1, wherein the composition is:   The composition of claim 1, wherein the one or more oligomeric phosphonates have a weight average molecular weight, determined by gel permeation chromatography in terms of polystyrene standards, of from about 500 g / mol to about 18,000 g / mol.   The composition of claim 1, wherein the one or more oligomeric phosphonates has a phosphorus content of about 2% to about 12% by weight.   The composition of claim 1, comprising about 5% to about 60% by weight of the one or more oligomeric phosphonates.   The one or more carbodiimides are N, N′-dicyclohexylcarbodiimide, N-cyclohexyl-N ′-(2-morpholinoethyl) carbodiimide meth-p-toluenesulfonate, bis (trimethylsilyl) carbodiimide, N- (3-dimethylamino Propyl) -N'-ethylcarbodiimide, N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide hydrochloride, 1,3-di-p-tolylcarbodiimide, N, N'-bis (2-methylphenyl) Carbodiimide, N- (tert-butyl) -N ′-[1- (2-chlorophenyl) -1-methylethyl] carbodiimide, N- (tert-butyl) -N ′-(2,6-dichlorophenyl) carbodiimide, N -Butyl-N '-[1- (2-chlorophenyl) -1-methyl Le] carbodiimide, N, N'-diisopropylcarbodiimide, dicyclohexylcarbodiimide, N- benzyl -N'- cyclohexyl carbodiimide, and is selected from the group consisting of The composition of claim 1.   The composition of claim 1, further comprising one or more antioxidants.   14. The composition according to claim 13, wherein the antioxidant is a hindered phenolic antioxidant or a phosphite antioxidant.   Chopped or continuous glass fiber, metal fiber, aramid fiber, carbon fiber, or ceramic fiber, surfactant, organic binder, polymer binder, crosslinking agent, diluent, coupling agent, flame retardant, anti-drip agent, Fluorinated polyolefin, silicone, lubricant, release agent, pentaerythritol tetrastearate, nucleating agent, antistatic agent, conductive black, carbon nanotube, graphite, graphene, graphene oxide, organic antistatic agent, polyalkylene ether, One selected from the group consisting of alkyl sulfonates, perfluorosulfonic acids, perfluorobutanes, potassium sulfonates, polyamide-containing polymers, catalysts, colorants, inks, dyes, antioxidants, stabilizers, and combinations thereof The method according to claim 1, further comprising the above additional components. The composition of the mounting. 16. The composition of claim 15 , comprising from about 0.001% to about 1% by weight of each individual additional component. A method for making an epoxy compound, comprising:
Combining an epoxy resin, a reactive phosphonate oligomer having one or more reactive end groups , from about 0.01% to about 4.0% by weight of carbodiimide, and a catalyst in a solvent to form a mixture;
Heating the mixture. 18. The method of claim 17 , wherein the step of heating is performed at a temperature from about 20C to about 250C. 18. The method of claim 17 , wherein the step of heating is performed for 60 minutes to 300 minutes. Heating is carried out at a pressure of about 3 × 103Pa~ about 1 × ¹⁰ -1 Pa, Process according to claim 17. 18. The method of claim 17 , wherein the catalyst is selected from the group consisting of a transition metal catalyst, a tertiary amine, an imidazole containing compound, and combinations thereof. The solvent is perfluorohexane, a, a, a-trifluorotoluene, pentane, hexane, cyclohexane, methylcyclohexane, decalin [c + t], dioxane, carbon tetrachloride, Freon-11, benzene, toluene, triethylamine, disulfide Carbon, diisopropyl ether, diethyl ether (ether), t-butyl methyl ether (MTBE), chloroform, ethyl acetate, 1,2-dimethoxyethane (glyme), 2-methoxyethyl ether (diglyme), tetrahydrofuran (THF), chloride Methylene, pyridine (Py), methyl ethyl ketone (MEK), acetone, hexamethylphosphoramide, N-methylpyrrolidinone, nitromethane, dimethylformamide, acetonitrile, sulfolane, dimethylsulfo Sid, and is selected from the group consisting of propylene carbonate The method of claim 17. An article of manufacture comprising an epoxy resin, one or more reactive oligomeric phosphonates having one or more reactive end groups, and about 0.01% to about 4.0% by weight of one or more carbodiimides. 24. The article of manufacture of claim 23 which is a prepreg or a laminate. 24. The manufacturing of claim 23 , wherein the manufacturing is selected from the group consisting of television, computer, laptop computer, tablet computer, printer, mobile phone, video game, DVD player, stereo, big data server, and consumer electronics. Goods.